Classifications

• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
  • A23L27/10—Natural spices, flavouring agents or condiments; Extracts thereof
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
  • A61K36/13—Coniferophyta (gymnosperms)
  • A61K36/14—Cupressaceae (Cypress family), e.g. juniper or cypress
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
  • A61K36/18—Magnoliophyta (angiosperms)
  • A61K36/185—Magnoliopsida (dicotyledons)
  • A61K36/73—Rosaceae (Rose family), e.g. strawberry, chokeberry, blackberry, pear or firethorn
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
  • A61K36/18—Magnoliophyta (angiosperms)
  • A61K36/185—Magnoliopsida (dicotyledons)
  • A61K36/73—Rosaceae (Rose family), e.g. strawberry, chokeberry, blackberry, pear or firethorn
  • A61K36/738—Rosa (rose)
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D11/00—Solvent extraction
  • B01D11/02—Solvent extraction of solids
  • B01D11/0203—Solvent extraction of solids with a supercritical fluid
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D11/00—Solvent extraction
  • B01D11/02—Solvent extraction of solids
  • B01D11/028—Flow sheets
  • B01D11/0284—Multistage extraction
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
  • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2236/00—Isolation or extraction methods of medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicine

Definitions

• the present invention relates to a process for obtaining a high-purity extract of juniper berries, sea buckthorn berries, rose hips or whitebeams, preferably juniper berries, by extraction with supercritical CO 2 .
• WO 2009/051606 A1 a method for the extraction of biopolymers from guayule ( Parthenium argentatum) and other rubber plants from the family of Asteraceae, Euphorbiceae, Campanulaceae, Labiatae and Moraceae.
• the extractant used is a combination of hexane and supercritical CO 2 .
• CN 102827129 and CN 103450135 describe the extraction of flavonols (betuletol or broussoflavonol A) and other natural substances from various plant species, including arnica, or even the bark of the paper mulberry tree ( Broussonetia papyrifera ) .
• the extraction itself is carried out with CO 2 , followed by the column chromatographic concentration of the extract.
• PL189884 B1 describes the extraction of walnut kernels with carbon dioxide and alcohol as cosolvent.
• EP 0 154 258 B1 describes the extraction of juniper and spices with supercritical gases such as CO 2 , N 2 O, butane, propane, ethane or ethylene. This document discusses that especially with this extraction material the problem of simultaneous unwanted extraction of substances that are found in the extract occurs. The removal of these undesirable substances in the extract (“degumming") reaches the EP 0 154 258 B1 in that CO 2 is added to the extractant as a co-solvent as entrainer (for example hexane or ethanol).
• entrainer for example hexane or ethanol
• An object of the present invention was therefore to provide a process for extracting, for example, juniper berries, which reduces the consumption of organic cosolvent and represents an improvement in ecological terms. In this case, the extraction efficiency should be equal to or even better than those described in the prior art.
• Wacholderex Track itself is loaded with organic Kosolvens, for example hexane, which must be removed by energy-intensive vacuum distillation in order to come to safe levels for further processing in food ( ⁇ 1000 ppm).
• organic Kosolvens for example hexane
• the further object of the present invention was therefore to provide an extraction process with which from these berries, especially juniper berries, as efficiently as possible, that is, in particular using very little extractant and energy, a sugar-free extract with low residual content of organic Solvent can be recovered.
• the invention offers over that in the EP 0 154 258 B1
• extraction methods described in juniper It is thus possible to obtain a berry extract which has a significantly lower content of sugar.
• the method also allows the more effective removal of mucilage with less consumption of organic and toxic solvents such as hexane or ethanol.
• an extraction residue B Ex is obtainable by the process according to the invention, which is not contaminated with cosolvent and can therefore be safely fed to composting.
• a juniper extract which is significantly less contaminated with organic solvent, such as hexane, even without an additional vacuum distillation step.
• berries B selected from the group consisting of rose hips, juniper, sea buckthorn, whitebeams are used. It is pointed out that these are not necessarily “berries” in the botanical sense - for the sake of simplicity, however, in the context of the invention for Rosehips, juniper berries, sea buckthorn berries, whitebeams used the collective term "berries B".
• the Sammelnussfr Chip the rose species (Rosa) to understand.
• the term "rosehip” in the context of the invention refers to the collection nut fruits of the following roses: dog rose (rosa canina ssp lito ), mountain rose ( rosa pendulina ) , potato rose ( rosa rugosa), scotch fern (rosa rubiginosa ) ,
• berries according to the invention are the berries of the plants of the genus Sorbus to understand.
• the term "whitebeam” refers to the berries of the following trees: rowan ( Sorbus aucuparia), lesser spotted sorbus (Sorbus domestica), and elderberry (Sorbus torminalis).
• Juniper for the purposes of the invention denotes all species of the genus Juniperus, in particular the common Juniper (Juniperus communis L.) and the Sweet Tree (Juniperus sabina).
• Sea buckthorn according to the invention refers to plants of the genus Hippophae, in particular Hippophae rhamnoides.
• “Flavorings” are the responsible for the characteristic taste and smell of the respective berries B chemical compounds. These flavors are formed by a few dozen to several hundred chemical compounds depending on the plant species. These chemical compounds are in particular hydrocarbons (terpenes and sesquiterpenes) and oxygenated compounds (alcohols, aldehydes, ketones, acids, phenols, lactones, acetals, ethers and esters).
• flavoring agents are in particular ⁇ -pinene, ⁇ -pinene, borneol, geraniol, sabinene (CAS numbers: 3387-41-5, 2009-00-9, 10408-16-9), 3-carene ( CAS numbers: 13466-78-9; 498-15-7). Some of these aromas are also found in rose hips, rowanberries and sea buckthorn berries.
• the optionally crushed berries are extracted with supercritical CO 2 without the addition of a cosolvent.
• the extraction with supercritical CO 2 is essential - with subcritical CO 2 sufficient extraction from the outset could not be achieved.
• the berries B are either crushed or crushed, but preferably crushed used. If the berries B crushed used, they are in particular in the step a. comminuted upstream step of the process according to the invention. For comminution, methods known to the person skilled in the art can be used, for example milling in the mill or squeezing in the roll mill.
• the minced or uncrushed berries B are extracted with supercritical CO 2 without the addition of a cosolvent.
• the supercritical CO 2 in particular has a temperature in the range of 31 ° C to ⁇ 100 ° C and a pressure in the range of 74 bar to 400 bar. Therefore, the step a.
• a temperature in the range 31 ° C to ⁇ 100 ° C and a pressure in the range of 74 bar to 400 bar carried out, preferably at a temperature in the range 40 ° C to 90 ° C and a pressure in the range of 100 bar to 350 bar, more preferably carried out at a temperature in the range 40 ° C to 70 ° C and a pressure in the range of 200 bar to 300 bar, more preferably at a temperature in the range 40 ° C to 50 ° C and a pressure in the range of 250 bar to 260 bar, most preferably carried out at 260 bar and 40 ° C.
• the extraction of the uncrushed or crushed berries B can be carried out by methods known to those skilled in the art. For example, describe the EP 0 154 258 B1 , the EP 0 200 150 , the DE 34 15 844 A1 and the EP 1 815 899 A1 corresponding devices for extraction using supercritical CO 2 .
• the supercritical CO 2 used in the process according to the invention is not particularly limited.
• the uncrushed or comminuted berries B used are in particular in the range from 1: 1 to 100: 1, preferably in the range from 10: 1 to 60: 1, more preferably in the range from 20: 1 to 45: 1.
• the process of the invention supercritical CO 2 is used without the addition of a Kosolvens.
• K is in particular selected from the group consisting of alkane, chlorinated alkane, alcohol, alkanecarboxylic acid ester, aliphatic ketone, aliphatic ether, water
• the total weight of all cosolvents K based on the weight of the supercritical used in step a CO 2 is less than 0.4% by weight, preferably less than 0.1% by weight, more preferably less than 0.01% by weight, more preferably "without the addition of a cosolvent” means that the total weight of all CO 2 different substances based on the weight of the supercritical CO 2 used in step a is less than 0.4% by weight, preferably less than 0.1% by weight, more preferably less than 0.01% by weight.
• the process according to the invention then gives a first extract comprising supercritical CO 2 and flavorings.
• the first extract comprises in particular mucilages and sugars, which were extracted from the berries B.
• a solid extraction residue B Ex is obtained, ie the extracted berries B. This can be the combustion or composting, in particular the composting, fed.
• the method according to the invention also encompasses the case in which during the extraction in step a. the process according to the invention in addition to the flavoring natural moisture from the berries B partially into the supercritical CO 2 passes and after performing step a.
• obtained first extract for example from the berries B mitextrahATORs water.
• the first extract may also comprise water, preferably less than 1% by weight, based on the total weight of CO 2 in the first extract.
• step a makes the process of the invention more economical and also results in an ecologically harmless extraction residue B Ex .
• a second step b At least a partial separation of CO 2 from the first extract is then carried out, whereby a second extract, which comprises the flavoring agents and a reduced amount of CO 2 compared with the first extract, is obtained.
• "At least partial deposition of CO 2 from the first extract” means in particular that at least 10% by weight, in particular at least 25% by weight, preferably at least 50% by weight, more preferably at least 75% by weight, more preferably at least 85% by weight, even more preferably at least 95% by weight, most preferably at least 98% by weight of the CO 2 contained in the first extract are removed therefrom.
• step b In the process according to the invention, the CO 2 is completely removed from the first extract, and a second extract is obtained which, in addition to the flavorings, in particular no longer comprises CO 2 .
• the deposition of the CO 2 can be done according to the expert procedure. In particular, this can be done simply by exposing the first extract to temperature-pressure conditions in which the CO 2 comprised by the first extract changes to the gaseous state, but the phase comprising the aroma substances is in the liquid state. By changing the pressure and / or temperature conditions, the solution properties of the gas also change, and the previously dissolved substances are then separated, for example, in a separating vessel.
• step b) of the method according to the invention.
• a temperature of 10 ° C to 80 ° C and a pressure of 10 bar to 65 bar more preferably one sets a temperature of 30 ° C to 60 ° C and a pressure of 40 bar to 60 bar, still more preferably a temperature of 30 ° C and a pressure of 45 bar to 50 bar.
• the separated CO 2 can then be converted back into the liquid state and transferred to a reservoir and then returned in the supercritical state in the extraction cycle (for example via a pump).
• the remaining second extract can then be released from the pressurized separator.
• a second extract which comprises the aroma substances and a reduced amount of CO 2 , preferably no CO 2 , compared to the first extract.
• the second extract in particular also contains mucilages and sugars which have been extracted from the berries B.
• the second extract obtained has the aroma substances and a reduced amount of CO 2 compared to the first extract, preferably the flavoring substances and no CO 2 .
• No CO 2 means that the content of CO 2 in step b. obtained second extract ⁇ 1 wt .-%, in particular ⁇ 0.1 wt .-%, preferably ⁇ 0.01 wt .-%, more preferably ⁇ 0.001 wt .-%, even more preferably ⁇ 0.0001 wt .-%, wherein wt .-% in in the case the total weight of the CO 2 contained in the second extract based on the total weight of the second extract.
• step c. of the inventive method is in step b.
• the second extract obtained is then extracted with an extractant selected from the group consisting of alkane, chlorinated alkane, alcohol, alkanecarboxylic acid ester, aliphatic ketone or aliphatic ether, whereby the extract E B is obtained.
• step b. obtained second extract in step c. of the inventive method then with an extractant selected from the group consisting of pentane, hexane, methylene chloride, dichloroethylene, trichlorethylene, methanol, ethanol, propanol, butanol, methyl acetate, ethyl acetate, isopropyl acetate, acetone, acetylacetone, dimethyl ether, diethyl ether, diisopropyl ether extracted.
• an extractant selected from the group consisting of pentane, hexane, methylene chloride, dichloroethylene, trichlorethylene, methanol, ethanol, propanol, butanol, methyl acetate, ethyl acetate, isopropyl acetate, acetone, acetylacetone, dimethyl ether, diethyl ether, diisopropyl ether extracted.
• step b. extract obtained in step c. of the inventive method then extracted with an extractant selected from the group consisting of hexane, ethanol, propanol, methyl acetate.
• an extractant selected from the group consisting of hexane, ethanol, propanol, methyl acetate.
• step b. extract obtained in step c. of the inventive method then extracted with an extractant selected from the group consisting of hexane, ethanol.
• step b. extract obtained in step c. of the inventive method then extracted with hexane.
• step c. of the method according to the invention in the extractant, which in step c. is used, while mucilage, sugar precipitate or remain behind in the residue.
• the phase formed by the extractant can then be separated from the residue.
• the organic solvent can be removed after separation by methods known to those skilled in the art (for example distillation), whereby the desired extract E B is obtained.
• the extractant used here is not particularly limited and is preferably 20: 1 to 1:20 (ratio of total weight of second extract to extractant), more preferably 1: 1 to 1:20, more preferably 1: 2 to 1:10, even more preferably 1: 3 to 1: 8, more preferably 1: 4 to 1: 6.
• step c. the method according to the invention, ie extraction of the in step b. Extract obtained, a third extract E B is obtained, which comprises the aroma of berries B selected from juniper berries, sea buckthorn berries, rose hips, whitebeams, but one opposite to that in the EP 0 154 258 B1 obtained extract has a lower sugar content.
• step c. it was found that the necessary removal of the mucilage in step c. can be achieved, wherein the combination of steps a. and c. the method according to the invention to achieve a degumming as large as in EP 0 154 258 B1 a much smaller amount of organic extractant is needed. This was also completely surprising.
• the process according to the invention can be carried out continuously or batchwise, but preferably continuously.
• Juniper berries crushed in a roller mill (70 kg) were filled in the autoclave and sealed.
• the autoclave was then pressed to 260 bar and the extraction temperature adjusted to 40 ° C. It is extracted from bottom to top in circulatory operation for 2 hours with supercritical CO 2 .
• the extract is collected in the separator. After the end of the extraction, first the water is drained off at the bottom of the separator, followed by the juniper extract.
• the extract obtained (8.6 kg) contains, among other things, fats, sugars, mucilage and flavorings and is cloudy.
• the residue of the extracted juniper berries can be fed to the composting.
• the extract obtained is stirred vigorously with four times the mass of hexane. After standing for 24 hours, the clear supernatant was fed to the thin film evaporator. Here was carried out under temperature and vacuum, the separation of the hexane from the juniper extract.
• the remaining sediment was again intensively stirred with twice the amount of hexane and allowed to stand until a clear supernatant was formed.
• the supernatant is filtered off and freed of hexane in a thin-film evaporator.
• the juniper extract is combined with the previous extract. The remaining sediment was fed to the combustion.
• Example 1 a) the EP 0 154 258 B1 Juniper berries crushed in a roller mill (60 kg) were filled in the autoclave and sealed. By means of a high-pressure pump, the autoclave was then pressed to 260 bar and the extraction temperature adjusted to 40 ° C. It was extracted from the bottom to the top in circulation operation with supercritical CO 2 , which was added in an entraining agent concentration of 3.4% hexane.
• the juniper extract was sedimented and filtered. In order to remove the hexane to a level of less than 1000 ppm (determined by gas chromatographic measurements), it was necessary to vacuum treat the extract at 65 ° C for three days. It was recovered 5.4 kg of juniper extract. The residue of the extracted juniper berries is loaded with hexane and must be sent to combustion. Composting is not possible for ecological reasons.
• the extract obtained in V1 is sweet, dark colored and highly viscous.
• the extract obtained in E1 is clearly clear, light green, less sweet and of low viscosity.

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Citations (14)

• 2015
  • 2015-07-22 EP EP15177806.5A patent/EP3120712B1/fr active Active

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